One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection
The photosensitized hole injection and guanine base damage phenomena have been investigated in the DNA sequence, 5′-d(CATG[subscript 1] [superscript Py]CG[subscript 2]TCCTAC) with a site-specifically positioned pyrene-like (Py) benzo[a]pyrene 7,8-diol 9,10-epoxide-derived N[superscript 2]-guanine ad...
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| Format: | Article |
| Language: | en_US |
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Wiley Blackwell
2014
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| Online Access: | http://hdl.handle.net/1721.1/88778 https://orcid.org/0000-0003-0011-3067 |
| _version_ | 1826193583204466688 |
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| author | Yun, Byeong Hwa Dedon, Peter C. Geacintov, Nicholas E. Shafirovich, Vladimir |
| author2 | Massachusetts Institute of Technology. Department of Biological Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Biological Engineering Yun, Byeong Hwa Dedon, Peter C. Geacintov, Nicholas E. Shafirovich, Vladimir |
| author_sort | Yun, Byeong Hwa |
| collection | MIT |
| description | The photosensitized hole injection and guanine base damage phenomena have been investigated in the DNA sequence, 5′-d(CATG[subscript 1] [superscript Py]CG[subscript 2]TCCTAC) with a site-specifically positioned pyrene-like (Py) benzo[a]pyrene 7,8-diol 9,10-epoxide-derived N[superscript 2]-guanine adduct (G[subscript 1] [superscript Py]). Generation of the Py radical cation and subsequent hole injection into the DNA strand by a 355 nm nanosecond laser pulses (∼4 mJ cm[superscript −2]) results in the transformation of G[subscript 1] [superscript Py] to the imidazolone derivative Iz[subscript 1] [superscript Py] and a novel G[subscript 1] [superscript Py*] photoproduct that has a mass larger by 16 Da (M+16) than the mass (M) of G[subscript 1] [superscript Py]. In addition, hole transfer and the irreversible oxidation of G[subscript 2], followed by the formation of Iz[subscript 2] was observed (Yun et al. [2007], J. Am. Chem. Soc., 129, 9321). Oxygen-18 and deuterium isotope labeling methods, in combination with an extensive analysis of the MS/MS fragmentation patterns of the individual dG[superscript Py*] nucleoside adduct and other data show that dG[superscript Py*] has an unusual structure with a ruptured cyclohexenyl ring with a carbonyl group at the rupture site and intact guanine and pyrenyl residues. The formation of this product competes with hole injection and thus diminishes the efficiency of oxidation of guanines within the oligonucleotide strand by at least 15% in comparison with that in the dG[superscript Py] nucleoside adduct. |
| first_indexed | 2024-09-23T09:41:24Z |
| format | Article |
| id | mit-1721.1/88778 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:41:24Z |
| publishDate | 2014 |
| publisher | Wiley Blackwell |
| record_format | dspace |
| spelling | mit-1721.1/887782022-09-26T13:08:06Z One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection Yun, Byeong Hwa Dedon, Peter C. Geacintov, Nicholas E. Shafirovich, Vladimir Massachusetts Institute of Technology. Department of Biological Engineering Dedon, Peter C. The photosensitized hole injection and guanine base damage phenomena have been investigated in the DNA sequence, 5′-d(CATG[subscript 1] [superscript Py]CG[subscript 2]TCCTAC) with a site-specifically positioned pyrene-like (Py) benzo[a]pyrene 7,8-diol 9,10-epoxide-derived N[superscript 2]-guanine adduct (G[subscript 1] [superscript Py]). Generation of the Py radical cation and subsequent hole injection into the DNA strand by a 355 nm nanosecond laser pulses (∼4 mJ cm[superscript −2]) results in the transformation of G[subscript 1] [superscript Py] to the imidazolone derivative Iz[subscript 1] [superscript Py] and a novel G[subscript 1] [superscript Py*] photoproduct that has a mass larger by 16 Da (M+16) than the mass (M) of G[subscript 1] [superscript Py]. In addition, hole transfer and the irreversible oxidation of G[subscript 2], followed by the formation of Iz[subscript 2] was observed (Yun et al. [2007], J. Am. Chem. Soc., 129, 9321). Oxygen-18 and deuterium isotope labeling methods, in combination with an extensive analysis of the MS/MS fragmentation patterns of the individual dG[superscript Py*] nucleoside adduct and other data show that dG[superscript Py*] has an unusual structure with a ruptured cyclohexenyl ring with a carbonyl group at the rupture site and intact guanine and pyrenyl residues. The formation of this product competes with hole injection and thus diminishes the efficiency of oxidation of guanines within the oligonucleotide strand by at least 15% in comparison with that in the dG[superscript Py] nucleoside adduct. National Institutes of Health (U.S.) (Grant R01 CA110261) 2014-08-18T18:23:16Z 2014-08-18T18:23:16Z 2010-04 2009-11 Article http://purl.org/eprint/type/JournalArticle 00318655 17511097 http://hdl.handle.net/1721.1/88778 Yun, Byeong Hwa, Peter C. Dedon, Nicholas E. Geacintov, and Vladimir Shafirovich. “One-Electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between Its Further Oxidation and DNA Hole Injection.” Photochemistry and Photobiology 86, no. 3 (January 22, 2010): 563–570. https://orcid.org/0000-0003-0011-3067 en_US http://dx.doi.org/10.1111/j.1751-1097.2010.00719.x Photochemistry and Photobiology Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Wiley Blackwell PMC |
| spellingShingle | Yun, Byeong Hwa Dedon, Peter C. Geacintov, Nicholas E. Shafirovich, Vladimir One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection |
| title | One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection |
| title_full | One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection |
| title_fullStr | One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection |
| title_full_unstemmed | One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection |
| title_short | One-electron Oxidation of a Pyrenyl Photosensitizer Covalently Attached to DNA and Competition Between its Further Oxidation and DNA Hole Injection |
| title_sort | one electron oxidation of a pyrenyl photosensitizer covalently attached to dna and competition between its further oxidation and dna hole injection |
| url | http://hdl.handle.net/1721.1/88778 https://orcid.org/0000-0003-0011-3067 |
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